EP3452538A1 - Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC POLYMER COMPRISING POLYSTYRENE - Google Patents

Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC POLYMER COMPRISING POLYSTYRENE

Info

Publication number
EP3452538A1
EP3452538A1 EP17723828.4A EP17723828A EP3452538A1 EP 3452538 A1 EP3452538 A1 EP 3452538A1 EP 17723828 A EP17723828 A EP 17723828A EP 3452538 A1 EP3452538 A1 EP 3452538A1
Authority
EP
European Patent Office
Prior art keywords
polystyrene
thermoplastic polymer
blowing agent
hfo
1336mzz
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17723828.4A
Other languages
German (de)
French (fr)
Inventor
Joseph Anthony Creazzo
Mark L. Robin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of EP3452538A1 publication Critical patent/EP3452538A1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • This invention relates to the use of Z-HFO-1336mzz as blowing agent for thermoplastic polymer comprising polystyrene.
  • WO 2008/1 18627 discloses the discovery of blowing agents that have a zero ODP and GWP of less than 50 and solubility in alkenyl polymers, notably polystyrene, that enable these blowing agents comprising more than 50 wt% of the total blowing agent to produce quality foam.
  • Quality foam is described as the foam having an average cell size of 0.02 to 5 mm, being close-celled, and having a density of 64 kg/m 3 or less. Indicia of lack of quality are small average cell size, density greater than 64 kg/m 3 , high open cell content and blowholes (p. 2, I. 9-13).
  • the quality foam is also essentially free of blowholes, which are described as being the size of multiple cell diameters and which can rupture at the foam surface to give an irregular surface (p. 2, I. 15-20).
  • the blowholes that do not rupture can be called macrovoids, and the irregular surface caused by the rupturing blowholes is the opposite of a smooth surface (skin).
  • One embodiment of the present invention is the process, and the foam produced by said process, comprising extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent comprising Z-HFO-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) under the conditions
  • melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
  • thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.
  • the process, and foam produced by said process comprises extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent consisting essentially of Z-HFO-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene (Z-HFO-
  • melt mixing being carried out under a pressure of at least 1500 psi (103 Bar)
  • extruding being carried out at a temperature of at least 120°C
  • extruding being carried out under a pressure of at least 1000 psi (69 Bar), said conditions being effective to produce closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.
  • the smooth skin indicates the absence of macrovoids and blowholes. Blowholes are macrovoids that have burst through the skin surface.
  • the closed cells are uniform in size and have an average cell size of 0.02 to 5 mm, indicating the absence of internal macrovoids.
  • the low density is preferably no greater than 48 kg/m 3 .
  • thermoplastic polymer comprising polystyrene is preferably high in molecular weight as indicated by their exhibiting a melt flow rate (sometimes called MFR or MFI) of no greater than 25 g/10 min as determined in accordance with the procedure of ASTM D 1238 at 200°C using a 5 kg weight on the molten polymer.
  • MFR melt flow rate
  • the combination of this preferred high molecular weight and the combination of conditions (a)-(d) enable the Z-HFO-1336mzz by itself as the sole blowing agent to produce the above-described foamed product even when the molten composition is free of any co-blowing agent.
  • co-blowing agent can be present in the molten composition in a minor amount relative to the amount of Z-HFO-1336mzz blowing agent present in the molten composition to contribute beneficially to the density and/or closed cell size of the foamed product.
  • co-blowing agent is present, the above-described conditions (a)-(d) are followed so that the extrusion process is still one in which above-described foamed product would be obtained, even when the density of the foamed product is no greater than 48 kg/m 3 , using Z-HFO- 1336mzz as the sole blowing agent.
  • the preferred molecular weight of the thermoplastic polymer comprising polystyrene is the preferred molecular weight of the thermoplastic polymer comprising polystyrene.
  • the conditions of operation (a)-(d) when co-blowing agent is present are such that the foam product described above for the present invention would be obtained even if co-blowing agent were not present.
  • the presence of co-blowing agent is unnecessary to obtain this foamed product.
  • the amount of Z-HFO-1336mzz is increased to replace the amount of co-blowing agent, whereby the total amount of blowing agent obtaining the foamed product is 100 wt% Z-HFO-1336mzz.
  • This embodiment of the present invention can be described as a process comprising extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent comprising Z-HFO- 1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) and co-blowing agent, under the conditions
  • composition being formed by melt mixing at a temperature of at least 180°C,
  • melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
  • a closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene said co-blowing agent being unnecessary to said Z-HFO-1336mzz (E-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) obtaining said closed cell, smooth skin, low density, preferably no greater than 48 kg/m 3 , foamed thermoplastic polymer comprising polystyrene under said conditions.
  • the Z-HFO-1336mzz obtains this result by itself, i.e. in the absence of the co-blowing agent.
  • thermoplastic polymer being foamed according to the present invention comprises polystyrene.
  • the polystyrene can be styrene homopolymer or can contain
  • thermoplastic polymer can also be a blend of polystyrene with other thermoplastic polymer.
  • the other thermoplastic polymer can also be a copolymer of styrene with monomer other than styrene.
  • a preferred monomer other than styrene is acrylonitrile.
  • thermoplastic polymer being foamed is polystyrene or blends of polystyrene with other thermoplastic polymer
  • styrene is preferably the dominant polymerized monomer (unit) in the thermoplastic polymer being foamed. More preferably, the polymerized units of styrene constitute at least 70 mol % or at least 80 mol% or at least 90 mol% or at least 100 mol% of the polymerized monomer units making up the thermoplastic polymer being foamed.
  • the amount of other monomer copolymerized with the styrene is such that the styrene content of the copolymer is at least 60 mol% of the copolymer, preferably at least 70 mol%, or at least 80 mol% or at least 90 mol% of the copolymer, based on the total mols (100%) making up the copolymer.
  • the styrene copolymer is the only styrene-containing polymer in the thermoplastic polymer or is a blend with other thermoplastic polymer, such as styrene homopolymer or other styrene copolymer.
  • thermoplastic polymer being foamed is entirely
  • polystyrene notably the styrene homopolymer.
  • the polystyrene component of this blend is preferably styrene homopolymer constituting at least 80 wt% of the combined weight of polystyrene and other thermoplastic polymer.
  • the molecular weight of the thermoplastic polymer comprising
  • polystyrene being foamed is sufficiently high to provide the strength necessary for the requirements of the foam application.
  • the strength requirement determines the minimum density of the foamed product.
  • the high molecular weight of the thermoplastic polymer comprising polystyrene also contributes to the strength of the foamed product.
  • An indicator of molecular weight is the rate at which the molten polymer flows through a defined orifice under a defined load. The lower the flow, the higher the molecular weight. Measurement of the melt flow rate is determined in accordance with ASTM D 1238 at 200°C and using a 5 kg weight on the molten polymer.
  • the weight of molten polymer flowing through the orifice in a defined amount of time enables the melt flow rate to be reported in g/10 min.
  • the melt flow rate of the thermoplastic polymer comprising polystyrene is no greater than 20 g/10 min, more preferably no greater than 15 g/10 min, and most preferably, no greater than 10 g/10 min.
  • the higher the molecular weight (lower the melt flow rate) the better the foaming result, especially with respect to the attainability of low density foamed products, while still achieving smooth skin on the foamed product.
  • the minimum melt flow rate for all the melt flow rates disclose herein is at least 1 g/10 min., whereby the melt flow rate ranges disclosed herein are 1 to 25, 1 to 20, 1 to15, and 1 to10, all values being g/10 min.
  • melt flow rate ranges disclosed herein are 1 to 25, 1 to 20, 1 to15, and 1 to10, all values being g/10 min.
  • thermoplastic polymer comprising polystyrene
  • thermoplastic polymer comprising polystyrene
  • thermoplastic polymer comprising polystyrene in the preceding paragraph can be replaced by the disclosure polystyrene.
  • Another embodiment of the invention is a foam product, comprising: a polymer matrix comprising a thermoplastic material selected from the group consisting of polystyrene, polystyrene copolymers, and blends of polystyrene with other thermoplastic polymers, defining a plurality of cells having an average cell size of from 0.02 to 5 mm, and a blowing agent comprising Z- HFO-1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene), having a density of less than 65 kg/m 2 , wherein the thermoplastic polymer has a melt flow rate of less than 25 g/ 10 min.
  • the molten composition being foamed can contain additives other than the polymer being foamed and the Z-HFO-1336mzz blowing agent, such as co-blowing agent, nucleating agent, flame retardant, cell stabilizer agent, surfactant, preservative colorant, antioxidant, reinforcing agent, filler, antistatic agent, IR attenuating agent, extrusion aid, plasticizer, viscosity modifier, and other known additives, all in the amount to obtain the effect desired.
  • additives other than the polymer being foamed can contain additives other than the polymer being foamed and the Z-HFO-1336mzz blowing agent, such as co-blowing agent, nucleating agent, flame retardant, cell stabilizer agent, surfactant, preservative colorant, antioxidant, reinforcing agent, filler, antistatic agent, IR attenuating agent, extrusion aid, plasticizer, viscosity modifier, and other known additives, all in the amount to obtain the effect desired.
  • the present invention is not limited
  • the co-blowing agent is preferably one having negligible ODP and low GWP, e.g. no greater than 150. If a co- blowing agent is used it may be selected from the group consisting of HFC- 152a, CO2, DME, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1224yd(E), HCFO-1224yd(Z) and HFO-1234yf.
  • the Z-HFO-1336mzz would constitute the major proportion of the total amount of blowing agent.
  • the Z-HFO- 1336mzz would constitute at least 60 wt% of the total blowing agent, preferably at least 70 wt%, with the co-blowing agent being present in the amounts of 40 wt% and 30 wt%, respectively.
  • its minimum amount will be as little as 5 wt% or 10 wt%, whereby the Z-HFO- 1336mzz will be present in the 95 wt% and 90 wt% amounts, respectively.
  • the preferred blowing agent composition when co-blowing agent is present is 90 to 75 wt% Z-HFO-1336mzz and 10 to 25 wt% of co-blowing agent.
  • nucleating agent examples include talc, graphite and
  • Examples of preferred flame retardants include tetrabromo-bis phenol A and polymeric flame retardants..
  • the molten composition is in effect the foamable composition.
  • the amount of blowing agent in the molten composition will depend on the amount of additives other than blowing agent and the density desired in the foamed product. Generally, the amount of blowing agent, whether Z-HFO- 1336mzz as the sole blowing agent or the Z-HFO-1336mzz blowing agent plus co-blowing agent, will be 5 to 25 wt%, based on the weight of the molten composition.
  • the process of the present invention is carried out using an extruder to form the molten composition and to extrude it to form the foamed product.
  • the steps (a)-(d) are practiced in and using an extruder.
  • the thermoplastic polymer comprising polystyrene forms the feed to the extruder.
  • the blowing agent(s) is (are) preferably fed into the extruder at a location intermediate to the feed and extrusion ends of the extruder, typically into the molten composition that is created as the extrusion screw advances the feeds to the extruder along its length.
  • the other additives to the molten composition are added where convenient and as may be dictated by the state of the additive.
  • solid additives can be conveniently be added to the feed end of the extruder, possibly as a mixture with the polymer feed in particulate form to the extruder.
  • the molten composition within the extruder is extruded through a die, thereby allowing the foamable composition to expand into a foamed product.
  • the foamed product which can be in such forms as sheet, plank, rod, or tube, is then cooled.
  • the present invention resides in certain conditions, unique to extrusion forming of thermoplastic polymers that include polystyrene, under which the extruder is operated.
  • the preferred temperature is at least 185°C, more preferably at least 190°C or at least 200°C or at least 210°C.
  • the preferred maximum temperature for all the melt mixing temperatures disclosed herein is 230°C.
  • the melt mixing temperatures disclosed herein are the temperatures of the melt in the mixing zone at the time of mixing.
  • the preferred pressure under which the melt mixing is carried out is at least 3000 psi (207 Bar), more preferably at least 3500 psi (241 Bar), more preferably at least 4000 psi (276 Bar).
  • the preferred maximum value for all the minimum pressures disclosed under which the melt mixing is carried out is no greater than 5000 psi (345 Bar).
  • the pressures disclosed herein are gauge pressures.
  • the molten composition is cooled so that the temperature at which the extrusion is carried out is preferably at least 125°C, more preferably at least 130°C.
  • the maximum value for all the minimum extrusion temperatures disclosed herein is preferably no greater than 140°C.
  • the extrusion temperatures disclosed herein are the temperature of the melt at the time of extrusion.
  • the extrusion is preferably carried out with a pressure of at least 1500 psi (103 Bar), more preferably at least 1600 psi (1 10 Bar).
  • the maximum value for the minimum extrusion pressures disclosed herein is preferably no greater than 2000 psi (138 Bar).
  • the extrusion pressure is the pressure inside the extrusion die.
  • melt mixing pressures of 3000 to 5000 psi (207 to 345 Bar) are preferred for achieving low foam densities of the foamed product, and this temperature range can be used with any of the melt mixing and extrusion temperature ranges to form any of the smooth-skin, closed cell foam product densities disclosed herein.
  • melt extrusion pressure range 1500 to 2000 psi (103 to 138 Bar) pressure range together with the 3000 to 5000 psi (207 to 345 bar) pressure range for melt mixing.
  • melt flow rates for the polymer being foamed of no greater than 25, 20, 15, and 10, and as little as at least 1 , all values being in g/10 min, can be used with any of these combinations of pressure and temperatures, depending on the foamed product result desired.
  • the conditions (a)-(d) can be used in any combination with any of the polymer melt flow rates and compositions and blowing agent compositions disclosed above.
  • thermoplastic polymer comprising polystyrene and polystyrene itself exhibits the following foamed product attributes: Closed cells - at least 80%, preferably at least 90% and most preferably at least 95%, and having an average cell size of 0.02 to 5 mm,
  • Density no greater than 40 g/m 3 and more preferably no greater than 35 kg/m 3 or 30 kg/m 3 , and
  • the minimum required strength (compressive) of the foamed product will dictate that the density be at least 16 kg/m 3 .
  • transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • the transitional phrase “consisting essentially of is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features,
  • This example demonstrates the use of Z-HFO-1336mzz blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam insulation.
  • the polystyrene used in this example is styrene homopolymer available as Nova 1600 polystyrene having a melt flow rate of 6 g/10 min.
  • This example demonstrates the use of Z-HFO-1336mzz blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam insulation.
  • the polystyrene used in this example is styrene homopolymer available as Nova 1600 polystyrene having a melt flow rate of 6 g/10 min.
  • This example demonstrates the use of Z-HFO-1336mzz/HFC-152a blend containing 77 wt% Z-HFO-1336mzz as the blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam
  • the polystyrene used in this example is styrene homopolymer available by Total Petrochemicals as PS 535B having a melt flow rate of 4 g/10 min.
  • a nucleating agent namely talc, is present along with the polystyrene and blowing agent in the molten composition formed within the extruder.
  • a 50 mm twin screw laboratory extruder was used with 9 individually controlled, electrically heated zones. The first four zones of the extruder were used to heat and soften the polymer. The remaining barrel sections, from the blowing agent injection location to the end of the extruder, were set at selected lower temperatures. An annular die with a 3 mm opening was used in extruding foamed rod specimens.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

A process is provided comprising extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent comprising Z-1,1,1,4,4,4-hexafluoro-2-butene (Z- HFO-1336mzz) under the conditions (a) said molten composition being formed by melt mixing at a temperature of at least 180°C, (b) said melt mixing being carried out under a pressure of at least 1500 psi (103 bar), (c) said extruding being carried out at a temperature of at least 120°C, and (d) said extruding being carried out under a pressure of at least 1000 psi (69 bar), said conditions being effective to produce closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.

Description

TITLE
Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC
POLYMER COMPRISING POLYSTYRENE
BACKGROUND INFORMATION
Field of the Disclosure
This invention relates to the use of Z-HFO-1336mzz as blowing agent for thermoplastic polymer comprising polystyrene.
Description of the Related Art
WO 2008/1 18627 (assigned to Dow Global Technologies) discloses the discovery of blowing agents that have a zero ODP and GWP of less than 50 and solubility in alkenyl polymers, notably polystyrene, that enable these blowing agents comprising more than 50 wt% of the total blowing agent to produce quality foam. Table 2 discloses HFO-1336mzz (CF3-CH=CH-CF3) having a moderate solubility as compared to the Table 1 compounds. It is further disclosed that while the alkenes of Table 2 can comprise over 50 wt% of the blowing agent composition, additional blowing agent that is more soluble in the polymer is necessary to achieve quality foam (p. 15, I. 9-12). Quality foam is described as the foam having an average cell size of 0.02 to 5 mm, being close-celled, and having a density of 64 kg/m3 or less. Indicia of lack of quality are small average cell size, density greater than 64 kg/m3, high open cell content and blowholes (p. 2, I. 9-13). The quality foam is also essentially free of blowholes, which are described as being the size of multiple cell diameters and which can rupture at the foam surface to give an irregular surface (p. 2, I. 15-20). The blowholes that do not rupture can be called macrovoids, and the irregular surface caused by the rupturing blowholes is the opposite of a smooth surface (skin).
SUMMARY
The present invention involves the discovery of foaming conditions different from those disclosed for practice of the invention in WO 2008/1 18627 that enable Z-CF3-CH=CH-CF3 (Z-HFO-1336mzz, Z- 1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) to be useful in foaming thermoplastic polymer comprising polystyrene, with the foamed product of the present invention being free of the indicia of non-quality foam, i.e. having smooth skin and not having macrovoids and/or blowholes.
One embodiment of the present invention is the process, and the foam produced by said process, comprising extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent comprising Z-HFO-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) under the conditions
(a) said molten composition being formed by melt mixing at a
temperature of at least 180°C,
(b) said melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
(c) said extruding being carried out at a temperature of at least 120°C, and
(d) said extruding being carried out under a pressure of at least 1000 psi (69 Bar),
said conditions being effective to produce closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.
In another embodiment of the invention, the process, and foam produced by said process, comprises extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent consisting essentially of Z-HFO-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene (Z-HFO-
1336mzz) under the conditions
(a) said molten composition being formed by melt mixing at a
temperature of at least 180°C,
(b) said melt mixing being carried out under a pressure of at least 1500 psi (103 Bar), (c) said extruding being carried out at a temperature of at least 120°C, and
(d) said extruding being carried out under a pressure of at least 1000 psi (69 Bar), said conditions being effective to produce closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.
The smooth skin indicates the absence of macrovoids and blowholes. Blowholes are macrovoids that have burst through the skin surface. The closed cells are uniform in size and have an average cell size of 0.02 to 5 mm, indicating the absence of internal macrovoids. The low density is preferably no greater than 48 kg/m3. These results are obtained by using the Z-HFO-1336mzz as the sole blowing agent in the molten composition.
The thermoplastic polymer comprising polystyrene is preferably high in molecular weight as indicated by their exhibiting a melt flow rate (sometimes called MFR or MFI) of no greater than 25 g/10 min as determined in accordance with the procedure of ASTM D 1238 at 200°C using a 5 kg weight on the molten polymer. The combination of this preferred high molecular weight and the combination of conditions (a)-(d) enable the Z-HFO-1336mzz by itself as the sole blowing agent to produce the above-described foamed product even when the molten composition is free of any co-blowing agent.
According to another embodiment of the present invention, co-blowing agent can be present in the molten composition in a minor amount relative to the amount of Z-HFO-1336mzz blowing agent present in the molten composition to contribute beneficially to the density and/or closed cell size of the foamed product. When co-blowing agent is present, the above-described conditions (a)-(d) are followed so that the extrusion process is still one in which above-described foamed product would be obtained, even when the density of the foamed product is no greater than 48 kg/m3, using Z-HFO- 1336mzz as the sole blowing agent. The same is true using the preferred molecular weight of the thermoplastic polymer comprising polystyrene. In other words, the conditions of operation (a)-(d) when co-blowing agent is present are such that the foam product described above for the present invention would be obtained even if co-blowing agent were not present. The presence of co-blowing agent is unnecessary to obtain this foamed product. According to this embodiment, the amount of Z-HFO-1336mzz is increased to replace the amount of co-blowing agent, whereby the total amount of blowing agent obtaining the foamed product is 100 wt% Z-HFO-1336mzz.
This embodiment of the present invention can be described as a process comprising extruding a molten composition comprising thermoplastic polymer comprising polystyrene and blowing agent comprising Z-HFO- 1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) and co-blowing agent, under the conditions
(a) said composition being formed by melt mixing at a temperature of at least 180°C,
(b) said melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
(c) said extruding being carried out at a temperature of at least 120°C, and
(d) said extruding being carried out under a pressure of at least 1000 psi (69 Bar), and
obtaining as a result thereof a closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene, said co-blowing agent being unnecessary to said Z-HFO-1336mzz (E-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) obtaining said closed cell, smooth skin, low density, preferably no greater than 48 kg/m3, foamed thermoplastic polymer comprising polystyrene under said conditions. The Z-HFO-1336mzz obtains this result by itself, i.e. in the absence of the co-blowing agent.
DETAILED DESCRIPTION The thermoplastic polymer being foamed according to the present invention comprises polystyrene.
The polystyrene can be styrene homopolymer or can contain
copolymerized monomer other than styrene, i.e. polystyrene copolymer. The thermoplastic polymer can also be a blend of polystyrene with other thermoplastic polymer. The other thermoplastic polymer can also be a copolymer of styrene with monomer other than styrene. A preferred monomer other than styrene is acrylonitrile.
Whether the thermoplastic polymer being foamed is polystyrene or blends of polystyrene with other thermoplastic polymer, styrene is preferably the dominant polymerized monomer (unit) in the thermoplastic polymer being foamed. More preferably, the polymerized units of styrene constitute at least 70 mol % or at least 80 mol% or at least 90 mol% or at least 100 mol% of the polymerized monomer units making up the thermoplastic polymer being foamed.
When the thermoplastic polymer contains styrene copolymer, the amount of other monomer copolymerized with the styrene, is such that the styrene content of the copolymer is at least 60 mol% of the copolymer, preferably at least 70 mol%, or at least 80 mol% or at least 90 mol% of the copolymer, based on the total mols (100%) making up the copolymer. This applies whether the styrene copolymer is the only styrene-containing polymer in the thermoplastic polymer or is a blend with other thermoplastic polymer, such as styrene homopolymer or other styrene copolymer.
Preferably, the thermoplastic polymer being foamed is entirely
polystyrene, notably the styrene homopolymer. When the thermoplastic polymer being foamed is a blend of polystyrene and other thermoplastic polymer as described above, the polystyrene component of this blend is preferably styrene homopolymer constituting at least 80 wt% of the combined weight of polystyrene and other thermoplastic polymer. The molecular weight of the thermoplastic polymer comprising
polystyrene being foamed is sufficiently high to provide the strength necessary for the requirements of the foam application. The strength requirement determines the minimum density of the foamed product. The high molecular weight of the thermoplastic polymer comprising polystyrene also contributes to the strength of the foamed product. An indicator of molecular weight is the rate at which the molten polymer flows through a defined orifice under a defined load. The lower the flow, the higher the molecular weight. Measurement of the melt flow rate is determined in accordance with ASTM D 1238 at 200°C and using a 5 kg weight on the molten polymer. The weight of molten polymer flowing through the orifice in a defined amount of time, enables the melt flow rate to be reported in g/10 min. Preferably the melt flow rate of the thermoplastic polymer comprising polystyrene is no greater than 20 g/10 min, more preferably no greater than 15 g/10 min, and most preferably, no greater than 10 g/10 min. Surprisingly the higher the molecular weight (lower the melt flow rate), the better the foaming result, especially with respect to the attainability of low density foamed products, while still achieving smooth skin on the foamed product. Preferably the minimum melt flow rate for all the melt flow rates disclose herein is at least 1 g/10 min., whereby the melt flow rate ranges disclosed herein are 1 to 25, 1 to 20, 1 to15, and 1 to10, all values being g/10 min. These molecular weights apply to the thermoplastic polymer comprising polystyrene in the molten composition whether the Z-HFO-1336mzz is the sole blowing agent present in the composition or whether co-blowing agent is also present.
The references to thermoplastic polymer comprising polystyrene also apply to polystyrene by itself. Thus, for example, the disclosure of
thermoplastic polymer comprising polystyrene in the preceding paragraph can be replaced by the disclosure polystyrene. Another embodiment of the invention is a foam product, comprising: a polymer matrix comprising a thermoplastic material selected from the group consisting of polystyrene, polystyrene copolymers, and blends of polystyrene with other thermoplastic polymers, defining a plurality of cells having an average cell size of from 0.02 to 5 mm, and a blowing agent comprising Z- HFO-1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene), having a density of less than 65 kg/m2, wherein the thermoplastic polymer has a melt flow rate of less than 25 g/ 10 min.
In other embodiments, the molten composition being foamed can contain additives other than the polymer being foamed and the Z-HFO-1336mzz blowing agent, such as co-blowing agent, nucleating agent, flame retardant, cell stabilizer agent, surfactant, preservative colorant, antioxidant, reinforcing agent, filler, antistatic agent, IR attenuating agent, extrusion aid, plasticizer, viscosity modifier, and other known additives, all in the amount to obtain the effect desired. The present invention is not limited to any particular additive, except as may be specified in any claim appended hereto.
To mention a few of these additives, the co-blowing agent, is preferably one having negligible ODP and low GWP, e.g. no greater than 150. If a co- blowing agent is used it may be selected from the group consisting of HFC- 152a, CO2, DME, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1224yd(E), HCFO-1224yd(Z) and HFO-1234yf.
If co-blowing agent were used, the Z-HFO-1336mzz would constitute the major proportion of the total amount of blowing agent. Thus, the Z-HFO- 1336mzz would constitute at least 60 wt% of the total blowing agent, preferably at least 70 wt%, with the co-blowing agent being present in the amounts of 40 wt% and 30 wt%, respectively. If co-blowing agent were used, its minimum amount will be as little as 5 wt% or 10 wt%, whereby the Z-HFO- 1336mzz will be present in the 95 wt% and 90 wt% amounts, respectively. Based on the combined weights of blowing agent totaling 100 wt%, the preferred blowing agent composition when co-blowing agent is present is 90 to 75 wt% Z-HFO-1336mzz and 10 to 25 wt% of co-blowing agent.
Preferred examples of nucleating agent are talc, graphite and
magnesium silicate. Examples of preferred flame retardants include tetrabromo-bis phenol A and polymeric flame retardants..
The molten composition is in effect the foamable composition. The amount of blowing agent in the molten composition will depend on the amount of additives other than blowing agent and the density desired in the foamed product. Generally, the amount of blowing agent, whether Z-HFO- 1336mzz as the sole blowing agent or the Z-HFO-1336mzz blowing agent plus co-blowing agent, will be 5 to 25 wt%, based on the weight of the molten composition.
The process of the present invention is carried out using an extruder to form the molten composition and to extrude it to form the foamed product. The steps (a)-(d) are practiced in and using an extruder. The thermoplastic polymer comprising polystyrene forms the feed to the extruder. The blowing agent(s) is (are) preferably fed into the extruder at a location intermediate to the feed and extrusion ends of the extruder, typically into the molten composition that is created as the extrusion screw advances the feeds to the extruder along its length. The other additives to the molten composition are added where convenient and as may be dictated by the state of the additive. For example, solid additives can be conveniently be added to the feed end of the extruder, possibly as a mixture with the polymer feed in particulate form to the extruder. The molten composition within the extruder is extruded through a die, thereby allowing the foamable composition to expand into a foamed product. The foamed product, which can be in such forms as sheet, plank, rod, or tube, is then cooled. The present invention resides in certain conditions, unique to extrusion forming of thermoplastic polymers that include polystyrene, under which the extruder is operated.
In the region within the extruder where the composition is melted to form the molten composition, this melting occurring by the input of heat and the heat developed in the mixing process forming the melt, this is considered the melt mixing region. The preferred temperature is at least 185°C, more preferably at least 190°C or at least 200°C or at least 210°C. The preferred maximum temperature for all the melt mixing temperatures disclosed herein is 230°C. The melt mixing temperatures disclosed herein are the temperatures of the melt in the mixing zone at the time of mixing. The preferred pressure under which the melt mixing is carried out is at least 3000 psi (207 Bar), more preferably at least 3500 psi (241 Bar), more preferably at least 4000 psi (276 Bar). The preferred maximum value for all the minimum pressures disclosed under which the melt mixing is carried out is no greater than 5000 psi (345 Bar). The pressures disclosed herein are gauge pressures.
In the region within the extruder where the molten composition is extruded, the molten composition is cooled so that the temperature at which the extrusion is carried out is preferably at least 125°C, more preferably at least 130°C. The maximum value for all the minimum extrusion temperatures disclosed herein is preferably no greater than 140°C. The extrusion temperatures disclosed herein are the temperature of the melt at the time of extrusion.
The extrusion is preferably carried out with a pressure of at least 1500 psi (103 Bar), more preferably at least 1600 psi (1 10 Bar). The maximum value for the minimum extrusion pressures disclosed herein is preferably no greater than 2000 psi (138 Bar). The extrusion pressure is the pressure inside the extrusion die.
The disclosures of multiple ranges for melt flow rate, temperature and pressure above can be used in any combination in the practice of the present invention to obtain the particular foamed structure desired. For example, melt mixing pressures of 3000 to 5000 psi (207 to 345 Bar) are preferred for achieving low foam densities of the foamed product, and this temperature range can be used with any of the melt mixing and extrusion temperature ranges to form any of the smooth-skin, closed cell foam product densities disclosed herein. The same is true for the melt extrusion pressure range of 1500 to 2000 psi (103 to 138 Bar) pressure range together with the 3000 to 5000 psi (207 to 345 bar) pressure range for melt mixing. Most preferably, the two preferred pressure ranges, for melt mixing (207 to 345 Bar) and extrusion (103 to 138 bar) are used together. The melt flow rates for the polymer being foamed of no greater than 25, 20, 15, and 10, and as little as at least 1 , all values being in g/10 min, can be used with any of these combinations of pressure and temperatures, depending on the foamed product result desired. The conditions (a)-(d) can be used in any combination with any of the polymer melt flow rates and compositions and blowing agent compositions disclosed above.
Preferably the thermoplastic polymer comprising polystyrene and polystyrene itself exhibits the following foamed product attributes: Closed cells - at least 80%, preferably at least 90% and most preferably at least 95%, and having an average cell size of 0.02 to 5 mm,
Density no greater than 40 g/m3 and more preferably no greater than 35 kg/m3 or 30 kg/m3, and
Smooth skin as described above. The minimum required strength (compressive) of the foamed product will dictate that the density be at least 16 kg/m3.
As used herein, the terms "comprises," "comprising," "includes,"
"including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features,
components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term 'consisting essentially of occupies a middle ground between
"comprising" and 'consisting of.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms "consisting essentially of" or "consisting of."
EXAMPLE 1 :
Polystyrene Foam Extrusion with Slit Die using Neat Z-HFO-1336mzz as the
Blowing Agent
This example demonstrates the use of Z-HFO-1336mzz blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam insulation. The polystyrene used in this example is styrene homopolymer available as Nova 1600 polystyrene having a melt flow rate of 6 g/10 min. A nucleating agent (nucleator), namely magnesium silicate, is present along with the polystyrene and blowing agent in the molten composition formed within the extruder.
For this example, a 30 mm twin screw laboratory extruder was used with 8 individually controlled, electrically heated zones and water cooled barrels. Extrusion used a slit die.
Table 1 - Extruder Operating Parameters and Foam Density Achieved
EXAMPLE 2:
Polystyrene Foam Extrusion with Round Die using Neat Z-HFO-1336mzz as the Blowing Agent
This example demonstrates the use of Z-HFO-1336mzz blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam insulation. The polystyrene used in this example is styrene homopolymer available as Nova 1600 polystyrene having a melt flow rate of 6 g/10 min. A nucleating agent (nucleator), namely magnesium silicate, is present along with the polystyrene and blowing agent in the molten
composition formed within the extruder
For this example, a 30 mm twin screw laboratory extruder was used with 8 individually controlled, electrically heated zones and water cooled barrels. Extrusion used a round die.
Table 2 - Extruder Operating Parameters and Foam Density Achieved
EXAMPLE 3:
Polystyrene Foam Extrusion using a 77/23 wt% Z-HFO-1336mzz/HFC- 152a Blend as the Blowing Agent
This example demonstrates the use of Z-HFO-1336mzz/HFC-152a blend containing 77 wt% Z-HFO-1336mzz as the blowing agent to produce polystyrene foam insulation exhibiting uniform closed cells, smooth skin, and low density. Macrovoids and blowholes are not present in the foam
insulation. The polystyrene used in this example is styrene homopolymer available by Total Petrochemicals as PS 535B having a melt flow rate of 4 g/10 min. A nucleating agent (nucleator), namely talc, is present along with the polystyrene and blowing agent in the molten composition formed within the extruder.
For this example, a 50 mm twin screw laboratory extruder was used with 9 individually controlled, electrically heated zones. The first four zones of the extruder were used to heat and soften the polymer. The remaining barrel sections, from the blowing agent injection location to the end of the extruder, were set at selected lower temperatures. An annular die with a 3 mm opening was used in extruding foamed rod specimens.
Table 3 - Extruder Operating Parameters and Foam Density Achieved

Claims

What is claimed is:
1 . Process comprising extruding a molten composition comprising
thermoplastic polymer comprising polystyrene and blowing agent comprising trans-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) under the conditions
(a) said molten composition being formed by melt mixing at a
temperature of at least 180°C,
(b) said melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
(c) said extruding being carried out at a temperature of at least 120°C, and
(d) said extruding being carried out under a pressure of at least 1000 psi (69 Bar),
said conditions being effective to produce closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene in the absence of any co-blowing agent.
2. Process of claim 1 wherein said low density is no greater than 48 kg/m3
3. Process of claim 1 wherein said melt mixing temperature is at least
185°C.
4. Process of claim 1 wherein said melt mixing pressure is at least 3000 psi (207 Bar).
5. Process of claim 1 wherein said extruding is at a temperature of at least 125°C.
6. Process of claim 1 wherein said extruding is under a pressure of at least 1500 psi (103 Bar).
7. Process of claim 1 herein said thermoplastic polymer comprising
polystyrene has a melt flow index of no greater than 25 g/10 sec.
8. Process of claim 1 wherein said thermoplastic polymer comprising polystyrene is polystyrene.
9. Process of claim 1 wherein said foamed thermoplastic polymer
comprising polystyrene has at least 80% closed cells. 10. The process of claim 1 wherein said molten composition comprises nucleating agent.
1 1 . The process of claim 10, wherein said nucleating agent comprises graphite.
12. The process of claim 1 , wherein said molten composition further
comprises a flame retardant.
13. The process of claim 12, wherein said flame retardant comprises a polymeric flame retardant.
14. The process of claim 1 wherein co-blowing agent is present in said molten composition and said Z-HFO-1336mzz comprises at least 60 wt% of the combined weight of said co-blowing agent and said Z-
HFO-1336mzz.
15. The process of claim 14, wherein said co-blowing agent comprises one or more co-blowing agents selected from the group consisting of HFC- 152a, XO2, DME, HFO-1234ze(E), HFO-1234ze(Z), HCFO-1233zd(E), HCFO-1233zd(Z), HCFO-1224yd(E), HCFO-1224yd(Z) and HFO-
1234yf.
16. The process of claim 14 wherein said foamed thermoplastic polymer comprising polystyrene is obtained under such conditions (a)-(d) as would result if said co-blowing agent were not present. 17. Process comprising extruding a molten composition comprising
thermoplastic polymer comprising polystyrene and blowing agent comprising Z-HFO-1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene) and co- blowing agent, under the conditions
(a) said composition being formed by melt mixing at a temperature of at least 180°C,
(b) said melt mixing being carried out under a pressure of at least 1500 psi (103 Bar),
(c) said extruding being carried out at a temperature of at least 120°C, and
(d) said extruding being carried out under a pressure of at least 1000 psi (69 Bar), and obtaining as a result thereof a closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene, said co-blowing agent being unnecessary to said Z-HFO-1336mzz (Z-1 , 1 ,1 ,4,4,4- hexafluoro-2-butene) obtaining said closed cell, smooth skin, low density foamed thermoplastic polymer comprising polystyrene under said conditions.
Process of claim 17 wherein said low density is no greater than 48 kg/m3.
A foam product comprising: a polymer matrix a thermoplastic material selected from the group consisting of polystyrene, polystyrene
copolymers, and blends of polystyrene with other thermoplastic polymers, defining a plurality of cells, and a blowing agent comprising Z- HFO-1336mzz (Z-1 , 1 , 1 ,4,4,4-hexafluoro-2-butene), having a density of less than 65 kg/m2, wherein the thermoplastic polymer has a melt flow rate of less than 25 g/ 10 min.
The foam product of claim 19 wherein the average cell size is between 0.02 μΜ and 500 μΜ.
The foam product composition of claim 19, wherein the thermoplastic polymer has a melt flow rate of less than 20 g/10 min.
22. The foam product composition of claim 19, wherein the thermoplastic polymer has a melt flow rate of less than 10 g/10 min.
23. The foam product composition of claim 19, wherein the thermoplastic polymer is polystyrene. 24. The foam product composition of claim 19, wherein the polystyrene copolymer is a copolymer of styrene and acrylonitrile.
EP17723828.4A 2016-05-06 2017-05-02 Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC POLYMER COMPRISING POLYSTYRENE Pending EP3452538A1 (en)

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019075040A1 (en) * 2017-10-10 2019-04-18 The Chemours Company Fc, Llc Process for the manufacture of thermoplastic foam containing hfo-1336mzz(z) and hfo-1336mzz(e)
PL3824021T3 (en) * 2018-07-16 2024-03-04 The Chemours Company Fc, Llc Blowing agent blends
EP3976700A1 (en) * 2019-05-29 2022-04-06 The Chemours Company FC, LLC Blowing agent blends for thermoplastic polymers
US20220235193A1 (en) * 2019-06-24 2022-07-28 The Chemours Company Fc, Llc Blowing agent blends for thermoplastic polymers
JP7141983B2 (en) * 2019-07-01 2022-09-26 旭有機材株式会社 Resin composition for producing phenolic foam, phenolic foam and method for producing the same
WO2021145417A1 (en) * 2020-01-16 2021-07-22 旭化成建材株式会社 Phenol resin foam laminated board and composite board
US12054596B2 (en) 2020-11-30 2024-08-06 Honeywell International Inc. Azeotrope or azeotrope-like compositions of Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z))
CA3228703A1 (en) * 2021-08-16 2023-02-23 Hayim Abrevaya Foamable thermoplastic compositions, thermoplastic foams and methods of making same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS597728B2 (en) * 1976-03-23 1984-02-20 旭ダウ株式会社 Method for manufacturing styrenic resin foam
CA2855233A1 (en) * 2005-11-01 2007-05-10 E.I. Du Pont De Nemours And Company Blowing agents for forming foam comprising unsaturated fluorocarbons
WO2008118627A2 (en) 2007-03-27 2008-10-02 Dow Global Technologies Inc. Alkenyl aromatic polymer foam comprising fluorinated alkene blowing agents
ES2376290T5 (en) * 2007-03-29 2020-03-19 Arkema Inc Use of blowing agent compositions based on hydrofluorolefins and hydrochlorofluorolefins for foaming thermoplastic material
ES2384007T3 (en) * 2007-07-03 2012-06-28 Dow Global Technologies Llc Closed cell foam with large cell size and high load content
SG176231A1 (en) * 2009-06-02 2011-12-29 Du Pont Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene
EP2706086A1 (en) * 2012-09-05 2014-03-12 Basf Se Method for manufacturing low density foam panels through the extrusion of styrol polymers using hydrofluoro-olefins as propellant
CN103172489B (en) * 2013-03-14 2015-07-15 巨化集团技术中心 Synthesis method of 1,1,1,4,4,4-hexafluorine-2-butene
CN106795310A (en) * 2014-07-10 2017-05-31 欧文斯科宁知识产权资产有限公司 The method for manufacturing extruded polystyrene foam body as main foaming agent using carbon dioxide

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